The C60‐pyridine, C60py, and C60‐imidazole, C60im, adducts were found to self‐assemble in films floating onto aqueous solutions of zinc tetrakis (N‐methylpyridinium)porphyrin cation, Zn(TMPyP), or zinc tetrakis (4‐sulfonatophenyl)porphyrin anion, Zn(TPPS). This self assembling was due to axial ligation of the C60 adducts (acceptors) by Zn
porphyrins (donors), which lead to the formation of relatively stable donor‐acceptor dyads in the water‐air interfaces. The films were compressed in a Langmuir trough and characterized by isotherms of surface pressure vs. area per molecule as well as by the Brewster angle microscopy imaging. All systems formed stable aggregated Langmuir
films of the “expanded liquid” type. Extensive compression of the films resulted in two‐dimensional phase transitions. The area per molecule at infinite dilution of the adducts in films increased in the order: water<0.1 mM Zn(TPPS)<0.1 mM Zn(TPMyP). Comparison of the determined and calculated values of area per molecule indicated that orientation of porphyrins in the complexes was parallel with respect to the interface plane. The Langmuir
films were transferred, by using the Langmuir‐Blodgett technique, onto quartz slides. The UV‐vis spectroscopic study of these films revealed that Zn
porphyrins were transferred together with the C60 adducts and that the transfer efficiency increased in the order: C60py‐Zn(TPPS)<C60py‐Zn(TMPyP)<C60im‐Zn(TPPS)<C60im‐Zn(TMPyP), i.e., in accord with the increase of stability of the respective dyads in solutions.

Endohedral fullerenes in general and cluster/molecule encapsulated endohedrals in particular exhibit a very complex dynamic behaviour, that has necessarily to be considered when investigating or characterizing these systems by spectrosopic measurements. Molecular dynamics (MD) simulations along with the calculation of dynamic spectra provide a detailed insight into the intra‐cage dynamics of these systems and help to clarify its impact on spectroscopic investigations. The effects are shown exemplarily for Sc3N@C80, Sc3N@C78 and Sc2C2@C84.

We present an AFM/STM analysis of an ionic C60 derivative, complemented by Raman measurements, light microscopy and mass spectrometry. It was previously demonstrated that this molecule self‐organizes into rod‐like structures. Our SPM investigations confirmed the formation of rods and revealed in detail a chiral fashion of the latter. The chirality is suggested to originate from the angle between the apolar C60 sphere and it’s charged functional group. On the micrometer scale superstructures could be observed which apparently originate from a dendritic growth process. The superstructures withstand heat treatment at 200 °C, but the functional groups are lost, and the remaining C60 undergoes a three dimensional polymerization.

Reduction of C70 with strontium dissolved in liquid ammonia results in metal fulleride solvates [Sr(NH3)8]3(C70)2 ⋅ nNH3 (n = 20−22) containing linear polymeric, anionic chains
. The compound was characterised by single crystal
structure determination. The accurate crystal structure, determined at atomic resolution, allowed a comparison with results of quantum chemical calculations. The detailed analysis of the bonding character reveals the preservation of the aromatic character of the phenylene‐type belt at the equator of C70 to be the driving force of this unexpected type of polymerisation.

Previous X‐Ray experiments have revealed the structure of the crystal thanks to the apparent immobility of the molecules. NMR studies demonstrate that the C60 molecules and the ferrocene molecules are in fact moving fast enough to average the magnetic interactions. This is shown by the temperature evolution of the resonance curve and by the shape of the CP‐MAS spectrum at room temperature. Further investigations allow to assert that the C60 molecules are undergoing 3D rotations and that Cp cycles of ferrocene are subject to planar rotations. Finally, analysis of the spectra at low MAS frequency leads to the conclusion that there are two kinds of Cp cycles.

Hydrofullerides with hydrogen content up to 5 Wt.% were obtained by direct and catalytic
reaction with H2 gas. Hydrogen content was monitored in situ using gravimetric system and verified by chemical analysis
ex situ. It was found that pure C60 reacts rapidly when exposed to H2 gas at 673 K and 50–100 Bar. Gravimetric study of this reaction showed that hydrogenation is saturated at about 5 at.% of hydrogen. Mass of the sample goes through a maximum and with a longer reaction time its weight start to decrease. This proves that hydrofullerides with high hydrogen content are not stable and strong hydrogenation results in collapse of C60 molecules. XRD study showed that samples prepared by direct hydrogenation without catalyst retain an original FCC structure with increase of cell parameter up to a=15.1Å. Catalytic hydrogenation of C60 with H2 gas results in decrease of the reaction temperature and formation of hydrofullerides with new crystal structure (suggestively sc).

The correlation times for the Jahn‐Teller dynamics of the
ions in the organic ferro‐magnet TDAE‐C60 have been extracted from a comparison of experimental and simulated 13C NMR lineshapes. A strong correlation between spin ordering and orientational ordering has been found.

Here we present preliminary results on Mg
4C60, a new fulleride polymer. A series of Mg
xC60 compositions were prepared by solid state synthesis. While most samples were multiphase, the nominal composition Mg
4C60 provided a single phase material. X‐ray powder diffraction data revealed that the structure is rhombohedral based on polymeric sheets of C60 molecules. Charge transfer from Mg to C60 was estimated by Raman microscopy.

Structure analysis of alkaline earth endohedral fullerenes M@C74 (M = Sr, Ba) has been performed by means of XANES and micro crystal synchrotron diffraction. The experimental results from XANES and simulations based on different exo‐ and endohedral model structures from ab‐initio calculations confirm the endohedral character of these compounds. The crystal structures of M@C74⋅Co(OEP)⋅2C6H6 (M = Sr, Ba) consist of (M@C74)[Co(OEP)]2(M@C74) units arranged in a distorted primitive hexagonal packing. The molecular structure is ordered and exhibits a high level of localization of the endohedral metal atom.

We report the spectroscopic work of two Ce‐containing incar‐fullerenes, iCeC82 and iCe2C80. UV/Vis, IR, Raman, TOF‐MALDI and 13C NMR were employed to investigate the structural and electronic information of these two major isomers of Ce incar‐fullerenes. Tumbling motion of two Ce atoms inside the Ih‐C80 cage was confirmed and analysed by temperature‐dependant 13C NMR.

Applying a recent photopolymerization method, we produced polymerized C60 in a gram scale and extracted different composition mixtures of its soluble components. We separated the oligomers by high‐performance liquid chromatography (HPLC). The major component of the soluble fractions is the (2+2) cycloadduct dimer, C120. Besides the dimer, we detected 3 different trimers and several higher oligomers including tetramers. The variation of the relative amounts of the trimers with the experimental conditions of polymerization is discussed in terms of the rate of formation and thermodynamic stability.

We have studied solution casted films of the major isomer of Dy@C82 (Dy@C82(I)) by cyclic voltammetry (CV) in acetonitrile. The films are found to display pronounced and stable redox response in the solution. A pair of reversible oxidation and rereduction waves is observed after the reoxidation of a reduced film. The characteristics and the inter‐relationship of these waves are uncovered by the CV technique, scanning electron microscopy
(SEM), and UV‐Vis‐NIR spectra.

The Jahn‐Teller effect plays a crucial role in the explanation of the insulating character of A4C60 (A = K, Rb, Cs). To detect possible phase transitions arising from the interplay between the molecular Jahn‐Teller distortion and the distorting potential field of the counterions, we measured the mid‐IR spectra of A4C60 compounds in the temperature range 90 – 300 K and found significant spectral changes with temperature in all three compounds. We also compare these spectra to that of Na
4C60 in its room‐temperature polymeric phase, where the distortion is more pronounced and evident from the structure.

The proposal of using the field‐effect for doping
organic crystals has raised enormous interest. To assess the feasibility of such an approach, we investigate the effect of a strong electric field on the electronic structure of C60 crystals. Calculating the polarization of the molecules and the splittings of the molecular levels as a function of the external field, we determine up to what field‐strengths the electronic structure of C60 stays essentially unchanged, so that one can speak of field‐effect doping, in the sense of putting charge carriers into otherwise unchanged states. Beyond these field strengths, the electronic structure changes so much, that on can no longer speak of a doped system. In addition, we address the question of a metal‐insulator transition at integer dopings and briefly review proposed mechanisms for explaining an increase of the superconducting transition temperature in field‐doped C60 that is intercalated with haloform molecules.

Ni‐ and Ce‐doped graphite
anodes were DC arced in helium and water to produce 1D nanocarbons. The products were analyzed by HR SEM and TEM techniques. The synergism of the binary catalysts used has been confirmed. Emission spectroscopy was performed to determine the temperature and C2 radical distributions in the arc.

Here we report synthesis and properties of SWNTs doped with organic molecules, such as TDAE and TCNQ. These organic molecules are well known by their strong ionization
energy or electronic affinity and have been used for organic charge transfer
compounds. The X‐ray profile of all samples strongly suggests encapsulation of molecules inside nanotubes. In optical absorption measurements, the reduction of absorption peak of semiconductive SWNTs was observed and this is understood by filling of the first DOS peak of the conducting band, providing direct evidence of charge (hole or electron) transfer between organic molecules and SWNTs.

A thermodynamic analysis of the carbon
nucleation on the metal surface was performed. The master equation for the dependence of critical radius of the carbon nucleus on the reaction parameters, such as the reaction temperature, the catalyst nature, the supersaturation degree of catalyst particle by carbon was obtained. This equation and the phase diagram approach were used for discussion of different scenarios of carbon deposits formation, namely, encapsulated particles, carbon fibers and filaments, multi‐wall and single‐wall carbon nanotubes.
Carbon filament growth via CO disproportionation on cobalt supported catalyst was investigated. Here we demonstrate the possibility to vary the reaction products using the same catalyst just changing the reaction conditions and catalysts pretreatment procedure. For the first time the formation of the carbon filament ropes on Co catalysts was observed.

The question of possible technological applications quickly aroused after the discovery of the unique physical properties of single‐walled carbon nanotubes
(SWCNTs). In this context, a wide range of initial approaches towards organic nanotube chemistry have been developed within the last few years. This also includes the covalent functionalization of the SWCNT sidewalls with nitrenes, carbenes or radicals, to increase solubility in organic solvents. With the use of bis‐alkoxycarbony‐lazides to create in‐situ di‐nitrenes, it should be possible to link individual SWCNTs and small bundles. The purpose of these experiments is to give the possibility for increasing the understanding of the chemical behaviour of SWCNTs and to provide further proofs for the occourance of this type of reaction. This can also be seen as a new way for forming nanotube
materials for exploiting their unique mechanical properties. The results obtained are discussed in this presentation. SEM,
XPS, XRD and Raman spectroscopy are used as characterization tools.

The nucleation of SWNTs is enhanced by early transition metals or rare earth catalysts. A mechanism is proposed on the basis of tight‐binding calculations in order to understand the growth mechanism of a nanotube on a metallic substrate. When electrons are transferred from the metal catalyst to the carbon atoms, the graphene sheet becomes unstable with respect to the formation of odd rings pentagon‐heptagon pairs in particular. Six such pairs auto‐assemble to build up the cap of a nanotube.